3,5-Ditertiary alkyl-4-hydroxyphenyl (alkyl) 6-acyloxy-4-thia hexanoates and hexenamides as antioxidants

ABSTRACT

Phenolic age resistors such as 4-(3,5-ditertiary butyl-4-hydroxyphenyl)-2-butyl 2-methyl-4-thia-6-octanoyloxyhexanoate are used as antioxidants in diene rubbers, such as butadiene-styrene types and in polyolefins, such as polypropylene.

This is a division of application Ser. No. 739,687 filed Nov. 8, 1976now U.S. Pat. No. 4,093,591.

BACKGROUND OF THE INVENTION

This invention relates to the preparation and use of phenolic ageresistors for polymers, both unsaturated and saturated. Moreparticularly, it concerns compounds comprised of a disubstitutedphenolic group attached at the para position to a carbon chaincontaining sulfur, a carbonyl group, and a carboxylic ester moiety.

The use of sulfur-containing hindered phenols is known, e.g., seeCanadian Pat. No. 904,339; U.S. Pat. No. Re. 27,004 and U.S. Pat. No.3,590,083 and British Pat. No. 1,396,469.

The art disclosing hindered phenols is extensive, including thosecontaining carbonyl or ester groups, see e.g. Japanese Pat. No.27,735/68, U.S. Pat. No. 3,753,943; U.S. Pat. No. 3,810,929, JapanesePat. No. 0468/63; Rubber Chemistry and Technology, Vol. 46, No. 1, Pp.96-105, March, 1973; U.S. Pat. No. 3,714,122 and Canadian Pat. No.812,262.

SUMMARY OF THE INVENTION

Among the objects of this invention are: (1) to provide phenolicantioxidants for the protection of polymers, (2) to provide polymersstabilized against oxidative degradation, and (3) to provide a processfor the preparation of said antioxidants. Other objects and advantageswill hereinafter appear.

The new compounds have the following general formula: ##STR1## wherein Rand R¹ are selected from the group consisting of tert. alkyl radicalshaving 4 to 8 carbons and cycloalkyl radicals having 5 to 12 carbons;R², R³, R⁴, R⁵, R⁶, R⁷ and R⁹ are selected from the group consisting ofH and alkyl radicals having 1 to 4 carbons; R⁸ is selected from thegroup consisting of alkyl radicals having 1 to 20 carbons, alkenylradicals having 2 to 20 carbons, cycloalkyl radicals having 5 to 12carbons, phenyl, substituted phenyl and aralkyl radicals having 7 to 12carbon atoms; x, y or z equals 0 to 12; x+y+z≦12; m equals 0 or 1; nequals 0 to 3 and X is 0 or NH.

The term "substituted phenyl" as used herein means a phenyl ring towhich is attached one or more radicals illustrated by but not limited tohalogens such as chlorine, alkyl radicals such as methyl, and hydroxyl.Preferably the substituted phenyl radical contains one or twosubstituents selected from the group consisting of methyl and otherlower alkyls.

These compounds can be used in free form to stabilize polymers againstoxidative degradation, and those in which R⁸ is 1-alkenyl can be used aspolymerizable antioxidants in diene polymers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The compounds of this invention are prepared by first reacting aβ-mercaptoethanol of structure ##STR2## with an unsaturated ester oramide of the structure ##STR3## The products of this reaction which areof the structure ##STR4## are then esterified by reaction with an acidchloride or anhydride derived from a carboxylic acid of the structure R⁸COOH. The first reaction is normally carried out in a low boilingalcohol, in the presence of a catalytic amount of a base, such as analkali metal hydroxide, a tertiary aliphatic amine, or a quaternaryammonium hydroxide at a temperature between room temperature and theboiling point of the solvent. The esterification is accomplished byadding an acid chloride or anhydride to a solution comprising theproducts of the first reaction; an acid acceptor, such as pyridine ortriethylamine and an aprotic solvent, such as ethyl ether,tetrahydrofuran, or carbon tetrachloride. Equimolar amounts of acidchloride (or anhydride) and the alcohol are preferred. The reaction,which is mildly exothermic, is normally carried out at ambienttemperature, but may be carried out at any temperature between 0° C. andthe boiling point of the solvent.

A typical preparation of one of this new class of compounds is shown inExample I which is intended to illustrate and not limit the methods bywhich the compounds of the present invention are made. Unless otherwiseindicated, all parts are parts by weight.

EXAMPLE I

A mixture of 12.5 grams of 3,5-ditert.butyl-4-hydroxyphenyl acrylate,3.5 grams of 2-mercaptoethanol, 0.25 grams of potassium hydroxide, and50 milliliters of ethanol was stirred at ambient temperature for 1-1/2hours. The reaction mixture was poured into water, and the oil whichprecipitated was separated by extraction with benzene. The benzene wasremoved on a rotary evaporator, leaving 16.0 grams of a viscous oilwhich was identified through its NMR spectrum as3,5-ditert.butyl-4-hydroxyphenyl 6-hydroxy-4-thiahexanoate. Thisproduct, along with 9.1 grams of triethylamine, was dissolved in 50milliliters of tetrahydrofuran. To this solution was added, over aperiod of 5 minutes, 5.7 grams of methacryloyl chloride. During theaddition, the temperature of the reaction mixture rose from 27° to 48°C. The reaction mixture was stirred for several hours and was thenpoured into water. The organic layer was separated by extraction withhexane. The hexane was removed on a rotary evaporator, leaving 17.2grams of a viscous yellow oil, identified as 3,5-ditert.butyl-4-hydroxyphenyl 6-methacryloxy-4-thiahexanoate.

Typical examples of the radicals and substituents are:

(1) R and R¹ when tertiary alkyl radicals can be, for example,1,1-dimethylpropyl; 1,1-dimethylbutyl; 1,1,2-trimethylpropyl;1,1-dimethylpentyl; 1,1-dimethylhexyl; 1,1,3-trimethylpentyl;1,1,3,3-tetramethylbutyl; 1-ethyl-1-methylbutyl; or tertiary butyl whichis preferred;

(2) R,R¹ and R⁸, when cycloalkyl radicals can be, for example,cyclopentyl; cyclohexyl; 2-methylcyclohexyl; 4-methylcyclohexyl;2,4-dimethylcyclohexyl; 4-tertiary butylcyclohexyl; or2-methylcyclopentyl;

(3) R², R³, R⁴, R⁵, R⁶, R⁷ and R⁹, when alkyl radicals can be forexample, methyl (which is preferred), ethyl, n-propyl, isopropyl,n-butyl or isobutyl;

(4) R⁸, when it is an alkyl radical can be, for example, those in number(3) above or pentyl, hexyl, octyl, 2-ethylhexyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, oreicosyl;

(5) R⁸, when it is a substituted phenyl can be, for example, p-tolyl;o-tolyl; p-ethylphenyl; p-isopropylphenyl; 2,4-xylyl; 3,5-xylyl;p-tert.butylphenyl; 2,4,6-trimethylphenyl; or 2,3,5-trimethylphenyl;

(6) R⁸, when it is an aralkyl radical can be, for example, benzyl;2-phenylethyl; p-methylbenzyl; 3-phenylpropyl; 2-phenylpropyl;p-tert.butyl benzyl; or 2,4-dimethylbenzyl; and

(7) R⁸, when it is an alkenyl radical can be, for example, vinyl andisopropenyl (preferred for polymerizable antioxidants); allyl,1-propenyl, 2-butenyl, 1-hexenyl, 2-methyl-2-propenyl, 1-octenyl,1-undecenyl, 3-methyl-1-heptenyl, 2-dodecenyl, 8-tridecenyl,8-heptadecenyl or 5-nonadecenyl.

Polymers susceptible to oxidative degradation in which theseantioxidants are beneficial include vulcanized and unvulcanized,saturated and unsaturated, natural and synthetic, homopolymers andcopolymers. The term "copolymer" as used herein, means a polymer whichis comprised of two or more different monomers. Representative examplesof each type are given for illustrative purposes; natural rubber in itsvarious forms, e.g. smoked sheet and balata; synthetic polymersincluding homopolymers (e.g. polyisoprene and polybutadiene),copolymers, e.g. styrene-butadiene rubbers, acrylonitrile-butadienerubbers, and copolymers of propylene, ethylene and dicyclopentadiene.Polyolefins such as polypropylene and polyethylene are also illustrativeof polymers which benefit by the practice of the present invention asare copolymers of ethylene and propylene.

Although the precise amount of antioxidant to be used depends on thepolymer and conditions to which it will be exposed, generally the amountemployed varies between 0.001 and 10 parts by weight per 100 parts byweight of polymer. A preferred range is about 0.05 to 1.75. Thecompounds are especially useful in polypropylene at a level of about 0.1parts per hundred as they possess superior resistance to discolorationby heat and ultraviolet light.

As free form antioxidants, the compounds of this invention may be addedto the polymer in any of the conventional ways, such as by addition tothe latex or to a solution of the polymer or by mixing with the drypolymer in a Banbury mixer or on a rubber mill.

The compounds can also be made to be an integral part of the polymeritself by either grafting or polymerization techniques. Being part ofthe polymer itself prevents the antioxidant from being volatilized orsolvent extracted from the polymer.

The grafting technique is accomplished by combining the antioxidant andthe polymer together in the presence of a free radical initiator. Theform in which the polymer is grafted (e.g., solution, latex or dry formsuch as on a mill or in a Banbury) can depend upon the free radicalinitiator being used. Free radical initiators include redox systems, azocompounds and peroxides.

The polymerization method involves the use of the antioxidant as amonomer in a free radical polymerization reaction. The formation of theresulting oxidation resistant polymer takes place during the normalsolution or emulsion polymerization reaction in which the principalmonomers combine in the presence of catalyst, solvent, modifier, andwhatever other emulsifiers and reagents are required for the preparationof the particular polymer. Conventional monomer systems andpolymerization recipes and techniques are disclosed or referenced inU.S. Pat. No. 3,714,122. The weight ratio of polymerizable antioxidantto the sum of the other monomers ranges from about 0.01 to 5 parts byweight of antioxidant to 100 parts by weight of other monomers. Thepreferred range is about 0.1 to 2 parts by weight per 100 parts of othermonomer. Preferably at least 50 parts by weight of the monomer systemconsists of a conjugated diene monomer such as 1,3-butadiene orisoprene.

Representative examples of the age resistors of this invention are:

1. 3,5-ditert.butyl-4-hydroxyphenyl 4-thia-6-methacryloxyhexanoate;

2. 3,5-ditert.butyl-4-hydroxyphenyl3-methyl-4-thia-6-methacryloxyhexanoate;

3. 3,5-ditert.butyl-4-hydroxyphenyl2-methyl-4-thia-6-benzoyloxyhexanoate;

4. 2-(3,5-ditert.butyl-4-hydroxybenzyloxy)ethyl4-thia-6-methacryloxyhexanoate;

5. 4-(3,5-ditert.butyl-4-hydroxyphenyl)-2-butyl4-thia-6-methacryloxyhexanoate;

6. 4-(3,5-ditert.butyl-4-hydroxyphenyl)-2-butyl2-methyl-4-thia-6-octanoyloxyhexanoate;

7.N-(3,5-ditert.butyl-4-hydroxyphenyl)-2-methyl-4-thia-6-methacryloxyhexanamide;

8. N-(3,5-ditert.butyl-4-hydroxybenzyl)-4-thia-6-methacryloxyhexanamide;

9.N-[1,1-dimethyl-2-(3,5-ditert.butyl-4-hydroxyphenyl)ethyl]-2-methyl-4-thia-6-methacryloxyhexanamide;

10.N-[1,1-dimethyl-2-(3,5-ditert.butyl-4-hydroxyphenyl)ethyl]-4-thia-6-isobutyroxyhexanamide;

11. 2,2-dimethyl-3-(3,5-ditert.butyl-4-hydroxyphenyl)propyl2-methyl-4-thia-6-acetoxyhexanoate;

12. 3,5-di-t-butyl-4-hydroxyphenyl 4-thia-6-stearoyloxyhexanoate;

13. 3,5-di-t-butyl-4-hydroxyphenyl 4-thia-6-oleoyloxyhexanoate;

14. 3,5-bis(1-methylcyclohexyl)-4-hydroxyphenyl2-methyl-4-thia-6-acetoxyhexanoate;

15. 2-ethyl-2-butyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propyl4-thia-6-acryloxyhexanoate;

16. 4-(3,5-di-t-butyl-4-hydroxyphenyl)-2-butyl 4-thia-6-(phenylacetoxy)hexanoate;

17. 4-(3,5-di-t-butyl-4-hydroxyphenyl)-2 -butyl4-thia-6-(4-methylbenzoyl) hexanoate.

For a better understanding of these complex structures, Table 1 isincluded, correlating the structures with the formulas of the examplecompounds:

                  Table 1                                                         ______________________________________                                        Correlation of Structure with Generic Formula                                  Com-                                                                         pound                                                                         No.   n     m     X    R.sup.5                                                                            R.sup.6                                                                            R.sup.8                                      ______________________________________                                        1     0     0     O    H    H                                                                                   ##STR5##                                    2     0     0     O    H    CH.sub.3                                                                            ##STR6##                                    3     0     0     O    CH.sub.3                                                                           H                                                                                   ##STR7##                                    4     1     1     O    H    H                                                                                   ##STR8##                                    5     0     1     O    H    H                                                                                   ##STR9##                                    6     0     1     O    CH.sub.3                                                                           H    C.sub.7 H.sub.15                             7     0     0     NH   CH.sub.3                                                                           H                                                                                   ##STR10##                                   8     0     1     NH   H    H                                                                                   ##STR11##                                   9     0     1     NH   CH.sub.3                                                                           H                                                                                   ##STR12##                                   10    0     1     NH   H    H    C(CH.sub. 3).sub.2                           11    0     1     O    CH.sub.3                                                                           H    CH.sub.3                                     12    0     0     O    H    H    (CH.sub.2).sub.16CH.sub.3                    13    0     0     O    H    H                                                                                   ##STR13##                                   14    0     0     O    CH.sub.3                                                                           H    CH.sub.3                                     15    0     1     O    H    H                                                                                   ##STR14##                                   16    0     1     O    H    H                                                                                   ##STR15##                                   17    0     1     O    H    H                                                                                   ##STR16##                                   ______________________________________                                    

The following examples illustrate the use of the compounds of thepresent invention as antioxidants and are not intended to be limitationsthereof.

In a test of some of these compounds as polymerizable antioxidants,butadiene/acrylonitrile/antioxidant terpolymers were prepared using thefollowing recipe:

    ______________________________________                                        Ingredient               Parts by Weight                                      ______________________________________                                        Butadiene                67                                                   Acrylonitrile            33                                                   Water                    195                                                  Potassium soap of tallow fatty acids                                                                   2.5                                                  Trisodium phosphate      0.2                                                  Ferrous sulfate          0.0144                                               *Chelating agent         0.0568                                               Sodium formaldehyde sulfoxylate                                                                        0.0412                                               Tert. dodecyl mercaptan  0.5                                                  **Cumene hydroperoxide (CHP)                                                                           0.023                                                Polymerizable Antioxidant                                                                              1.5                                                  ______________________________________                                         *90/10 mixture of tetrasodium salt of ethylenediaminetetraacetic acid and     monosodium salt of N,Ndi(αN-di(α-hydroxyethyl)glycine.            **70% cumene hydroperoxide in cumene.                                    

The resulting polymers were coagulated, extracted 48 hours with methanolin a Soxhlet extractor, dried, and dissolved in benzene. Films were castfrom the benzene solutions and oxygen absorption measurements were madeon the films. The results of these measurements are listed in Table 2.

                  Table 2                                                         ______________________________________                                        Oxygen Absorption of NBR (CHP Initiator)                                      Containing Bound Antioxidant                                                  Compound     Hours to Absorb 1% O.sub.2 @ 100° C.                      ______________________________________                                        1            65                                                               2            97                                                               4            80                                                               5            38                                                               7            265                                                              8            151                                                              9            149                                                              ______________________________________                                    

Two butadiene/acrylonitrile rubbers were prepared from monomer systemscontaining one of the compounds of the present invention.Azoisobutyronitrile was used as the initiator. The polymers wereextracted and oxygen absorption measurements made. The results arelisted below:

                  Table 3                                                         ______________________________________                                        Compound     Hours to Absorb 1% O.sub.2 @ 100° C.                      ______________________________________                                        5            238                                                              9            265                                                              ______________________________________                                    

Table 4 contains additional data on samples of emulsion polybutadieneprepared from a monomer system containing 1.5 parts by weight of apolymerizable antioxidant per 100 parts by weight of butadiene.

                  Table 4                                                         ______________________________________                                        Compound     Hours to Absorb 1% O.sub.2 @ 100° C.                      ______________________________________                                        1            283                                                              5            257                                                              7            313                                                              8            209                                                              9            246                                                              ______________________________________                                    

Compounds 1 through 11 were each used in free form to stabilize an SBRpolymer (1006) by addition to a benzene solution of SBR-1006 at aconcentration of 1 part per 100 parts rubber. Oxygen absorption testswere made on the films by evaporation of the benzene. The testingprocedure is of the type described in further detail in Industrial andEngineering Chemistry, Vol. 43, page 456 (1951) and Industrial andEngineering Chemistry, Vol. 45, p. 392 (1953).

Oven aging tests at 140° C. were also carried out on samples ofpolypropylene at 0.1 parts by weight free form antioxidant per 100 partsby weight polypropylene. The tests of the compounds used as free formantioxidants are presented in Table 5.

                  Table 5                                                         ______________________________________                                                      Hours to Absorb                                                                              Days to Failure                                                1% Oxygen      at 140° C. in                             Compound      SBR-1006       Polypropylene                                    ______________________________________                                        1             715            --                                               2             773            --                                               3             467            15                                               4             638            --                                               5             676            10                                               6             589            21                                               7             485             8                                               8             850            --                                               9             960            --                                               10            538            13                                               11            633            --                                               Commercial Phenolic                                                           Antioxidant   --             39                                               ______________________________________                                    

The antioxidants of this invention are equal or superior to commerciallyavailable products in discoloration characteristics. Several commercialcontrols and several of the compounds of this invention were mixed atthe 0.1 pph level into polypropylene. Original color and color of theplastic after five days oven exposure at 140° C. was measured to testthermal discoloration resistance. The results are shown in Table 6.

                                      Table 6                                     __________________________________________________________________________            Original Color                                                                            Aged 5 days @ 140° C.                              Compound                                                                              Rd a  b  CI*                                                                              Rd  a  b    CI*                                           __________________________________________________________________________    No Anti-                                                                      oxidant 51.6                                                                             -1.3                                                                             +5.8                                                                             7.3                                                                              Failed                                                                            -- --   --                                            3       53.3                                                                             -1.7                                                                             +5.6                                                                             7.3                                                                              51.1                                                                              -1.6                                                                             +5.3 7.0                                           5       55.3                                                                             -1.2                                                                             +6.0                                                                             7.7                                                                              53.5                                                                              -1.3                                                                             +5.7 7.6                                           6       53.0                                                                             -1.4                                                                             +6.2                                                                             7.0                                                                              53.2                                                                              -1.5                                                                             +6.6 6.6                                           7       53.0                                                                             -1.5                                                                             +7.5                                                                             5.9                                                                              48.1                                                                              -1.5                                                                             +10.8                                                                              3.9                                           10      53.2                                                                             -2.8                                                                             +4.5                                                                             4.5                                                                              49.7                                                                              -3.5                                                                             +12.8                                                                              3.8                                           Commercial                                                                    Phenolic                                                                      Antioxidant                                                                   Control 1                                                                             56.0                                                                             -1.5                                                                             +6.1                                                                             7.4                                                                              53.4                                                                              -1.6                                                                             +6.4 6.7                                           Commercial                                                                    Polycyclic                                                                    Antioxidant                                                                   Control 2                                                                             54.4                                                                             -1.7                                                                             +6.0                                                                             7.1                                                                              49.4                                                                              -1.6                                                                             +6.5 6.1                                           Commercial                                                                    Control 3                                                                             52.8                                                                             -1.7                                                                             +5.8                                                                             7.0                                                                              49.9                                                                              -1.7                                                                             +7.4 5.5                                           Wingstay L                                                                            52.7                                                                             -1.7                                                                             +7.5                                                                             5.7                                                                              43.7                                                                              -4.4                                                                             +30.6                                                                              1.2                                           __________________________________________________________________________     *CI is Color Index                                                       

Three of the experimental antioxidants (3, 5 and 6) were as good orbetter than the commercial controls, and all of them were superior toWingstay L.

Ultraviolet light discoloration and stain tendencies were measured in anSBR based test formulation at the 1.5 pphr level. Measurements weretaken of the original color of the rubber compounds and color after 120hours Fade-O-Meter exposure both with and without a coating of whitenitrocellulose lacquer on the samples. This lacquer manifests stainingtendencies. The results of these discoloration tests are shown in Table7.

                                      Table 7                                     __________________________________________________________________________            Original Color                                                                            Fade-O-Meter Exposed                                                                      Fade-O-Meter Exposed                                  Tinting     120 hrs. discoloration                                                                    120 hrs. - stain                              Compound                                                                              Rd a  b  CI*                                                                              Rd a  b  CI*                                                                              Rd  a  b   CI*                                __________________________________________________________________________    No AO   87.8                                                                             -0.8                                                                             +5.1                                                                             14.9                                                                             88.1                                                                             -0.8                                                                             +4.7                                                                             16.0                                                                             91.3                                                                              -0.3                                                                             +3.6                                                                              23.4                               3       88.0                                                                             -0.9                                                                             +5.3                                                                             14.2                                                                             87.6                                                                             -1.3                                                                             +6.6                                                                             11.1                                                                             91.1                                                                              -0.3                                                                             +4.2                                                                              20.2                               5       88.2                                                                             -0.9                                                                             +5.3                                                                             14.2                                                                             87.9                                                                             -0.8                                                                             +5.6                                                                             13.7                                                                             91.3                                                                              -0.2                                                                             +3.6                                                                              24.0                               6       89.2                                                                             -0.9                                                                             +5.6                                                                             13.7                                                                             89.7                                                                             -0.8                                                                             +5.3                                                                             14.5                                                                             91.5                                                                              -0.3                                                                             +3.9                                                                              21.8                               7       89.3                                                                             -1.2                                                                             +7.2                                                                             10.6                                                                             88.0                                                                             -0.5                                                                             +6.3                                                                             12.4                                                                             91.1                                                                              -0.2                                                                             +3.8                                                                              22.8                               10      89.0                                                                             -0.8                                                                             +5.0                                                                             15.3                                                                             88.7                                                                             -0.9                                                                             +5.3                                                                             14.3                                                                             91.3                                                                              -0.2                                                                             +4.0                                                                              21.7                               Wingstay L                                                                            87.6                                                                             -0.9                                                                             +6.1                                                                             12.5                                                                             87.3                                                                             -1.3                                                                             +7.2                                                                             10.3                                                                             91.2                                                                              -0.3                                                                             +4.0                                                                              21.2                               Commercial                                                                    Antioxidant                                                                   Control 87.2                                                                             -1.2                                                                             +6.5                                                                             11.3                                                                             82.6                                                                             -0.4                                                                             +9.4                                                                             8.4                                                                              **85.4                                                                            -0.3                                                                             13.4                                                                               6.2                               __________________________________________________________________________     *CI is Color Index                                                            **Visual stain at 48 hours                                               

All of the experimental materials exceeded Wingstay L and the othercontrol in discoloration resistance, and only compound 7 and thecommercial control appeared to tint the original color slightly.

In Tables 6 and 7 color measurements are based on the Hunter CoordinateSystem in which an Rd of 100 is perfect reflectance and an Rd of 0 is ablack body (perfect absorbance). Positive a represents red; negative agreen; positive b yellow; and negative b blue. The greater the absolutevalue of a or b, the greater is the intensity of color.

Color Index is Rd/(|a|+|b|). The greater the color index, the closercolor is to white.

The preferred reaction temperature for the reaction between theunsaturated ester or amide and the β-mercaptoethanol depends on theparticular ester or amide used. Generally, the reaction proceeds well atthe reflux temperature of the solvent (78° C. in the case of ethanol).The amount of base used is generally less than five moles per 100 molesof reactants, preferably less than one mole per 100 moles of reactants.The two reactants are preferably present in stoichiometric amounts, i.e.equimolar, although other ratios can be utilized.

Examples of unsaturated esters and amides which can be used in the firstreaction are:

3,5-ditert.butyl-4-hydroxyphenyl acrylate

3,5-ditert.butyl-4-hydroxyphenyl 2-butenoate

3,5-ditert.butyl-4-hydroxyphenyl methacrylate

3,5-ditert.butyl-4-hydroxyphenyl methacrylamide

3,5-ditert.butyl-4-hydroxyphenyl acrylamide

Examples of the solvents which may be used are: ethanol, methanol and1-propanol.

Examples of the bases which may be used are: potassium hydroxide, sodiumhydroxide, triethylamine, and trimethyl benzyl ammonium hydroxide.

The acid acceptor in the esterification reaction is used in amountsequimolar with the acid chloride, although some excess can be used.Equimolar amounts of acid chloride (or anhydride) and the alcohol arepreferred, although different ratios may be used and a 10 percent excessof acid chloride over the equimolar amount is sometimes desirable.

Examples of acid chlorides and anhydrides which may be used are aceticanhydride; acetyl chloride, methacryloyl chloride; isobutyryl chloride;acryloyl chloride; methylbenzoyl chloride and benzoic anhydride.

While certain representative embodiments and details have been shown forthe purpose of illustrating the invention, it will be apparent to thoseskilled in this art that various changes and modifications may be madetherein without departing from the spirit or scope of the invention.

What is claimed is:
 1. A process for making compounds having thefollowing structural formula: ##STR17## wherein R and R¹ are radicalsselected from the group consisting of tert. alkyl radicals having from 4to 8 carbons, and cycloalkyl radicals having from 5 to 12 carbons; R²and R³ are selected from the group consisting of H, and alkyl radicalshaving from 1 to 4 carbons; R⁴, R⁵, R⁶, R⁷ and R⁹ are selected from thegroup consisting of H and alkyl radicals having from 1 to 4 carbons; R⁸is selected from the group consisting of alkyl radicals having from 1 to20 carbons, alkenyl radicals having from 2 to 20 carbons, cycloalkylradicals having from 5 to 12 carbons, phenyl, substituted phenyl, andaralkyl radicals having from 7 to 12 carbon atoms; x, y or z equals 0 to12; x+y+z≦12; m equals 0 or 1; n equals 0 to 3; an X is 0 or NH; whichprocess comprises:(a) reacting a β-mercaptoethanol of the structure##STR18## with an unsaturated ester or amide of the structure ##STR19##in a low boiling polar solvent, in the presence of a catalytic amount ofbase at a temperature between room temperature and the boiling point ofthe solvent; (b) combining an acid chloride or anhydride derived from acarboxylic acid of the structure R⁸ COOH with a solution comprising thereaction product of (a) which is of the structure ##STR20## an acidacceptor and an aprotic solvent; (c) maintaining the resulting reactionin (b) at a temperature between 0° C. and the boiling point of thesolvent; and (d) separating the compound of structure (I) above bystandard physical unit operations.
 2. A compound having the followingstructural formula: ##STR21## wherein R and R¹ are radicals selectedfrom the group consisting of tert. alkyl radicals having from 4 to 8carbons, and cycloalkyl radicals having from 5 to 12 carbons; R² and R³are selected from the group consisting of H, and alkyl radicals havingfrom 1 to 4 carbons; R⁴, R⁵, R⁶, R⁷ and R⁹ are selected from the groupconsisting of H and alkyl radicals having from 1 to 4 carbons; R⁸ isselected from the group consisting of alkyl radicals having from 1 to 20carbons, alkenyl radicals having from 2 to 20 carbons, cycloalkylradicals having from 5 to 12 carbons, phenyl, substituted phenyl, andaralkyl radicals having from 7 to 12 carbon atoms; x, y or z equals 0 to12; x+y+z≦12; m equals 0 or 1; and n equals 0 to
 3. 3. A compound havingthe following structural formula: ##STR22## wherein R and R¹ areradicals selected from the group consisting of tert. alkyl radicalshaving from 4 to 8 carbons, and cycloalkyl radicals having from 5 to 12carbons; R² and R³ are selected from the group consisting of H, andalkyl radicals having from 1 to 4 carbons; R⁴, R⁵, R⁶, R⁷ and R⁹ areselected from the group consisting of H and alkyl radicals having from 1to 4 carbons; R⁸ is selected from the group consisting of alkyl radicalshaving from 1 to 20 carbons, alkenyl radicals having from 2 to 20carbons, cycloalkyl radicals having from 5 to 12 carbons, phenyl,substituted phenyl, and aralkyl radicals having from 7 to 12 carbonatoms; x, y or z are integers from 0 to 12; 1<(x+y+z)≦12; m equals 0 or1; n equals 0 to 3; and X is 0 or NH, with the proviso that if n=0, m is1, and if m=0, n is 1-3.